U.S. patent number 9,845,445 [Application Number 14/634,923] was granted by the patent office on 2017-12-19 for cleaning compositions comprising alkoxylated polyalkyleneimine, organomodified silicone and silixane-based diluent.
This patent grant is currently assigned to The Procter & Gamble Company. The grantee listed for this patent is The Procter & Gamble Company. Invention is credited to Bernard William Kluesener, Rebecca Ann Langevin, Fei Li, Rajan Keshav Panandiker, Sherri Lynn Randall, Gang Si, Yu Zhao.
United States Patent |
9,845,445 |
Li , et al. |
December 19, 2017 |
Cleaning compositions comprising alkoxylated polyalkyleneimine,
organomodified silicone and silixane-based diluent
Abstract
The present invention relates to cleaning compositions with
improved rinse suds profile, which comprise an alkoxylated
polyalkyleneimine, an organomodified silicone and a siloxane-based
diluent.
Inventors: |
Li; Fei (Beijing,
CN), Zhao; Yu (Beijing, CN), Panandiker;
Rajan Keshav (West Chester, OH), Kluesener; Bernard
William (Harrison, OH), Langevin; Rebecca Ann (Norwood,
OH), Randall; Sherri Lynn (Hamilton, OH), Si; Gang
(Beijing, CN) |
Applicant: |
Name |
City |
State |
Country |
Type |
The Procter & Gamble Company |
Cincinnati |
OH |
US |
|
|
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
54367276 |
Appl.
No.: |
14/634,923 |
Filed: |
March 2, 2015 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20150322380 A1 |
Nov 12, 2015 |
|
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
PCT/CN2015/073284 |
Feb 26, 2015 |
|
|
|
|
61991649 |
May 12, 2014 |
|
|
|
|
62028965 |
Jul 25, 2014 |
|
|
|
|
62044447 |
Sep 2, 2014 |
|
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D
1/72 (20130101); C11D 3/3723 (20130101); C11D
3/3738 (20130101); C11D 1/722 (20130101); C11D
3/0026 (20130101); C11D 1/66 (20130101); C11D
3/162 (20130101); C11D 3/30 (20130101); C11D
3/373 (20130101); C11D 1/14 (20130101); C11D
1/22 (20130101); C11D 3/124 (20130101); C11D
1/88 (20130101) |
Current International
Class: |
C11D
1/02 (20060101); C11D 1/66 (20060101); C11D
3/00 (20060101); C11D 3/12 (20060101); C11D
1/722 (20060101); C11D 1/22 (20060101); C11D
1/72 (20060101); C11D 1/14 (20060101); C11D
1/88 (20060101); C11D 3/30 (20060101); C11D
3/16 (20060101); C11D 3/37 (20060101) |
Field of
Search: |
;510/336,337,466,499
;134/25.2 ;8/137 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
WO 2012/075685 |
|
Jun 2012 |
|
WO |
|
Other References
US. Appl. No. 14/631,908, filed Feb. 26, 2015, Rajan Keshav
Panandiker, et al. cited by applicant .
Search Report for International Application No. PCT/CN2015/073284,
dated May 11, 2016, 12 pages. cited by applicant.
|
Primary Examiner: Delcotto; Gregory R
Attorney, Agent or Firm: Darley-Emerson; Gregory S. Lewis;
Leonard W. Miller; Steve W.
Claims
What is claimed is:
1. A cleaning composition comprising: (a) at least one alkoxylated
polyalkyleneimine comprising a polyalkyleneimine core and at least
one side chain bonded to a nitrogen atom in the polyalkyleneimine
core, wherein the polyalkyleneimine core has an average
number-average molecular weight (MWn) ranging from 100 to 100,000
Daltons, and wherein said at least one side chain has an empirical
formula (I) of: -(EO).sub.b(PO).sub.c--R (I) wherein: EO is
ethylene oxide; b has a weight average value ranging from 3 to 60;
PO is propylene oxide; c has a weight average value ranging from 0
to 60; R is selected from the group consisting of hydrogen,
C.sub.1-C.sub.4 alkyls, and combinations thereof; (b) an
organomodified silicone comprising one or more aryl moieties each
comprising a 5- to 9-membered aromatic ring, wherein said aromatic
ring can be either substituted or unsubstituted, either
heteroatomic or homoatomic, either monocyclic or multicyclic; and
(c) from about 0.001 wt % to about 10 wt % of a siloxane-based
diluent comprising a first polydimethylsiloxane having a first,
higher viscosity and a second polydimethylsiloxane having a second,
lower viscosity, and wherein the weight ratio of said first
polydimethylsiloxane to said second polydimethylsiloxane is greater
than 1:1, said diluent having a Solubility Index of from 0.8 to
1.25 in said organomodified silicone.
2. The cleaning composition of claim 1, comprising a first
alkoxylated polyalkyleneimine having a polyalkyleneimine core with
Mwn ranging from 100 to 5000 Daltons; b ranges from 10 to 50; and
wherein c ranges from 1 to 50.
3. The cleaning composition of claim 2, further comprising a second
alkoxylated polyalkyleneimine having a polyalkyleneimine core with
Mwn ranging from 100 to 5000 Daltons; b ranges from 5 to 40; and
wherein c is 0.
4. The cleaning composition of claim 3, wherein the weight ratio
between said first and second alkoxylated polyalkyleneimines ranges
from 1:10 to 10:1.
5. The cleaning composition of claim 1, comprising said at least
one alkoxylated polyalkyleneimine in an amount ranging from 0.01 wt
% to 20 wt %.
6. The cleaning composition of claim 1, wherein the aromatic ring
of said one or more aryl moieties in said organomodified silicone
is selected from the group consisting of phenyl, furan, pyrrole,
thiophene, imidazole, pyrazole, oxazole, pyridine, pyrazine,
naphthalene, anthracene moieties, and derivatives thereof.
7. The cleaning composition of claim 1, wherein said organomodified
silicone further comprises one or more C.sub.2-C.sub.20 aliphatic
moieties.
8. The cleaning composition of claim 1, wherein said organomodified
silicone comprises from 1 mol % to 75 mol % of siloxane units
containing a 2-phenylpropyl moiety; and from 1 mol % to 20 mol % of
siloxane units containing a C.sub.3-C.sub.30 aryl moiety.
9. The cleaning composition of claim 1, comprising said
organomodified silicone in an amount ranging from 0.001 wt % to 10
wt %.
10. The cleaning composition of claim 1, wherein said
siloxane-based diluent has a Solubility Index of from 0.85 to 1.2
in said organomodified silicone.
11. The cleaning composition of claim 1, wherein said
siloxane-based diluent has a viscosity, at a shear rate of 20
sec.sup.-1 and 25.degree. C., ranging from 0.5 cSt to 10,000
cSt.
12. The cleaning composition of claim 1, wherein the first, higher
viscosity ranges from 8 cSt to 12 cSt, and wherein the second,
lower viscosity ranges from 5 cSt to 10 cSt, when measured at a
shear rate of 20 sec.sup.-1 and 25.degree. C.
13. The cleaning composition of claim 1, further comprising: (d) a
hydrophobically modified silica, which is present in said cleaning
composition in an amount ranging from 0.0001 wt % to 1 wt %; (e) a
silicone resin, which is present in said cleaning composition in
amount ranging from 0.0001 wt % to 1 wt %; and (f) optionally, a
solvent for the silicone resin that is present in said cleaning
composition in an amount ranging from 0 wt % to 0.5 wt %.
14. The cleaning composition of claim 1, further comprising one or
more surfactants selected from the group consisting of anionic
surfactants, nonionic surfactants, cationic surfactants, amphoteric
surfactants, zwitterionic surfactants, and combinations
thereof.
15. The cleaning composition of claim 14, comprising from 1 wt % to
50 wt % of one or more anionic surfactants selected from the group
consisting of C.sub.10-C.sub.20 linear alkyl benzene sulphonates,
C.sub.10-C.sub.20 linear or branched alkylethoxy sulfates having an
average degree of ethoxylation ranging from 0.1 to 5.0,
C.sub.10-C.sub.20 linear or branched alkyl sulfates,
C.sub.10-C.sub.20 linear or branched alkyl ester sulfates,
C.sub.10-C.sub.20 linear or branched alkyl sulphonates,
C.sub.10-C.sub.20 linear or branched alkyl ester sulphonates,
C.sub.10-C.sub.20 linear or branched alkyl phosphates,
C.sub.10-C.sub.20 linear or branched alkyl phosphonates,
C.sub.10-C.sub.20 linear or branched alkyl carboxylates, and
combinations thereof.
16. The cleaning composition of claim 15, further comprising from
0.05 wt % to 20 wt % of one or more nonionic surfactants selected
from the group consisting of C.sub.8-C.sub.18 alkyl alkoxylated
alcohols having a weight average degree of alkoxylation ranging
from 1 to 20 and combinations thereof.
17. The cleaning compositions of claim 15, comprising no more than
3 wt % of soaps and no more than 3 wt % of nonionic
surfactants.
18. The cleaning composition of any of claim 15, further comprising
from 0.5 wt % to 20 wt % of one or more amphoteric surfactant
and/or zwitterionic surfactant.
19. A consumer product comprising the cleaning composition
according to claim 1, wherein said consumer product is a fabric and
home care product.
20. A liquid detergent composition comprising: (a) from 1 wt % to 5
wt % of at least one alkoxylated polyalkyleneimine comprising a
polyalkyleneimine core and at least one side chain bonded to a
nitrogen atom in the polyalkyleneimine core, wherein the
polyalkyleneimine core has an average number-average molecular
weight (MWn) ranging from 200 to 1000 Daltons, and wherein said at
least one side chain has an empirical formula (I) of:
-(EO).sub.b(PO).sub.c--R (I) wherein: EO is ethylene oxide; b has a
weight average value ranging from 20 to 30; PO is propylene oxide;
c has a weight average value ranging from 10 to 30; R is hydrogen;
(b) from 0.02 wt % to 0.5 wt % of an organomodified silicone, which
comprises from 10 mol % to 40 mol % of siloxane units containing a
2-phenylpropyl moiety and from 3 mol % to 10 mol % of siloxane
units containing a C.sub.6-C.sub.10 alkyl moiety; (c) from 0.02 wt
% to 0.5 wt % of a siloxane-based diluent comprising a first
polydimethylsiloxane having a first, higher viscosity and a second
polydimethylsiloxane having a second, lower viscosity, and wherein
the weight ratio of said first polydimethylsiloxane to said second
polydimethylsiloxane is greater than 1:1, said diluent having a
Solubility Index of from 0.85 to 1 in said organomodified silicone;
(d) from 0.002 wt % to 0.05 wt % of a hydrophobically modified
silica; (e) from 0.002 wt % to 0.05 wt % of a silicone resin; (f)
from 5 wt % to 30 wt % of an anionic surfactant selected from the
group consisting of C.sub.10-C.sub.20 linear alkyl benzene
sulphonates, C.sub.10-C.sub.20 linear or branched alkylethoxy
sulfates having an average degree of ethoxylation ranging from 0.5
to 3, methyl ester sulfonates with a C.sub.10-C.sub.20 linear or
branched alkyl group, and combinations thereof; (g) optionally,
from 0.5 wt % to 20 wt % of an amphoteric surfactant and/or a
zwitterionic surfactant; (h) optionally, from 0.1 wt % to 10 wt %
of a nonionic surfactant; and (i) water.
21. A method of washing fabric or dishes to achieve optimized rinse
suds profile, said method comprising contacting the composition
according to claim 1 with said fabric or dishes.
22. The method of claim 21, wherein said contacting comprises
handwashing said fabric or dishes.
Description
FIELD OF THE INVENTION
The present invention relates to cleaning products, and preferably
to liquid laundry or dish detergent products. The cleaning products
of the present invention contain an alkoxylated polyalkyleneimine,
an organomodified silicone and a siloxane-based diluent, which in
combination exhibit surprising and unexpected improvements in their
ability to reduce suds during the rinse cycle of a cleaning
process.
BACKGROUND OF THE INVENTION
Surfactants in detergent products typically create a significant
volume of suds during wash. During subsequent rinsing steps, the
suds and excessive surfactants are rinsed off together with soil
and other debris.
Sudsing profile of a detergent composition is important for the
consumer experience, where the appropriate volume and speed of suds
formation, retention and disappearance in the wash and rinse cycles
are considered key benchmarks of cleaning performance by the
consumers.
A large volume of suds is initially desirable, especially during a
hand washing process where the user is directly involved with the
wash, feeling and touching the suds generated by the detergent
composition. Copious suds during the wash is viewed by the
consumers as the primary and most desirable signal of cleaning, as
it indicates to the user that sufficient surfactant is present,
working to clean the articles (e.g., fabric or dishes).
Paradoxically, while a large volume of suds is desirable during the
wash cycle of a cleaning process, it is nevertheless undesirable
during the rinse cycle. If a high volume of suds is still present
during the rinse cycle, the consumers immediately infer from it
that there may still be surfactant residue left on the articles and
that the articles are not yet "clean". As a result, the consumers
will feel the need to rinse multiple times until the suds
completely disappear. Sometimes, it can take between 3-6 rinses in
order to remove such suds to the satisfaction of the consumer. This
adds up to a greater consumption of water. Typically, about 5-10
tons of water is consumed per year per household in countries such
as India and China, where habits of hand-washing fabric or dishes
are more prevalent than machine-washing. Because water is often a
limited resource, especially in those hand-washing countries, the
excess amount of water consumed by multiple rinses reduces the
amount of water available for other possible uses, such as
irrigation, drinking, bathing, etc.
However, it has been found that fewer rinses can sufficiently
remove surfactants, and thus multiple rinses are not necessary.
Therefore, if the above-described consumer perception can be
successfully overcome, the number of rinsing can be reduced with
little or no adverse effects to the end cleaning result.
Various foam-control or anti-foaming agents have been added to
detergent or cleaning compositions to control and reduce suds
volume. For example, U.S. Pat. No. 8,536,109 (Dow Corning)
discloses a foam control composition that contains a silicone
anti-foam dispersed in an organopolysiloxane resin, wherein the
silicone anti-foam includes an organopolysiloxane, an organosilicon
resin, and a hydrophobic filler; U.S. Pat. No. 7,566,750 (Wacker)
discloses a defoamer composition containing an organopolysiloxane,
filler particles and/or an organopolysiloxane resin, and a very
minor amount of added water, which is more effective in reducing
the foam or suds volume.
There is a continuing need for improved foam control or
anti-foaming agents that can further reduce suds, especially those
that can more effectively suppress or kill suds during the rinse
cycle of a cleaning process, to thereby minimize the amount of
water needed for rinse, and preferably to enable "single rinse" of
the to-be-cleaned article. Cleaning compositions containing such
improved foam control or anti-foaming agents are particularly
desirable for cost saving and environmental conservation
purposes.
SUMMARY OF THE INVENTION
The present invention discovers that a cleaning composition,
especially a liquid detergent composition, which contains the
combination of an alkoxylated polyalkyleneimine with an
organomodified silicone having one or more aryl moieties and a
siloxane-based diluent having a Solubility Index of from about 0.8
to about 1.25 in the organomodified silicone (measured according to
the test method described hereinafter), exhibits surprising and
unexpected synergistic effect in reducing rinse suds volume.
In one aspect, the present invention relates to a cleaning
composition containing: (a) an alkoxylated polyalkyleneimine
comprising a polyalkyleneimine core and at least one side chain
bonded to a nitrogen atom in the polyalkyleneimine core, while the
polyalkyleneimine core has an average number-average molecular
weight (MWn) ranging from about 100 to about 100,000 Daltons, and
such at least one side chain has an empirical formula (I) of:
-(EO).sub.b(PO).sub.c--R (I) while EO is ethylene oxide; b has a
weight average value ranging from about 3 to about 60; PO is
propylene oxide; c has a weight average value ranging from 0 to
about 60; R is selected from the group consisting of hydrogen,
C.sub.1-C.sub.4 alkyls, and combinations thereof; (b) an
organomodified silicone comprising one or more aryl moieties each
including a 5- to 9-membered aromatic ring, while the aromatic ring
can be either substituted or unsubstituted, either heteroatomic or
homoatomic, either monocyclic or multicyclic; and (c) a
siloxane-based diluent having a Solubility Index of from about 0.8
to about 1.25 in the organomodified silicone.
In a preferred embodiment of the present invention, the cleaning
composition further contains hydrophobically modified silica, a
silicone resin, and optionally an emulsifier.
The cleaning composition of the present invention may further
contain one or more surfactants selected from the group consisting
of anionic surfactants, nonionic surfactants, cationic surfactants,
amphoteric surfactants, zwitterionic surfactants, and combinations
thereof. The cleaning composition of the present invention
preferably forms a fabric and home care product, preferably a
liquid detergent product, and more preferably a liquid laundry or
dish detergent product.
In another aspect, the present invention relates to a liquid
detergent composition containing: (a) from about 1 wt % to about 5
wt % of an alkoxylated polyalkyleneimine comprising a
polyalkyleneimine core and at least one side chain bonded to a
nitrogen atom in the polyalkyleneimine core, while the
polyalkyleneimine core has an average number-average molecular
weight (MWn) ranging from about 200 to about 1000 Daltons, and
while the at least one side chain has an empirical formula (I) of
-(EO).sub.b(PO).sub.c--R, given that EO is ethylene oxide; b has a
weight average value ranging from about 20 to about 30; PO is
propylene oxide; c has a weight average value ranging from about 10
to about 30; and R is hydrogen; (b) from about 0.02 wt % to about
0.5 wt % of an organomodified silicone, which contains from about
10 mol % to about 40 mol % of siloxane units containing a
2-phenylpropyl moiety and from about 3 mol % to about 10 mol % of
siloxane units containing a C.sub.6-C.sub.10 alkyl moiety; (c) from
about 0.02 wt % to about 0.5 wt % of a siloxane-based diluent
having a Solubility Index of from about 0.85 to about 1 in the
afore-mentioned organomodified silicone; (d) from about 0.002 wt %
to about 0.05 wt % of a hydrophobically modified silica; (e) from
about 0.002 wt % to about 0.05 wt % of a silicone resin; (f) from
about 5 wt % to about 30 wt % of an anionic surfactant; (g)
optionally, from about 0.5 wt % to about 20 wt % of an amphoteric
surfactant and/or zwitterionic surfactant; (h) optionally, from
about 0.1 wt % to about 10 wt % of a nonionic surfactant; and (i)
water.
Still another aspect of the present invention relates to the use of
the liquid detergent composition as described hereinabove for
washing fabric or dishes, and preferably for hand-washing fabric or
dishes, to achieve optimized rinse sudsing profile.
These and other features of the present invention will become
apparent to one skilled in the art upon review of the following
detailed description when taken in conjunction with the appended
claims.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
As used herein, the articles "a" and "an" when used in a claim, are
understood to mean one or more of what is claimed or described.
As used herein, the terms "comprising," "comprises," "include",
"includes" and "including" are meant to be non-limiting.
As used herein, the term "substantially free of" or "substantially
free from" means that the indicated material is present in an
amount of no more than about 5 wt %, preferably no more than about
2%, and more preferably no more than about 1 wt %.
As used therein, the term "essentially free of" or "essentially
free from" means that the indicated material is at the very minimal
not deliberately added to the composition, or preferably not
present at an analytically detectible level in such composition. It
may include compositions in which the indicated material is present
only as an impurity of one or more of the materials deliberately
added to such compositions.
As used herein, the term "solid" includes granular, powder, bar and
tablet product forms.
As used herein, the term "fluid" includes liquid, gel, paste and
gas product forms.
As used herein, the term "liquid" refers to a fluid having a liquid
having a viscosity of from about 1 to about 2000 mPa*s at
25.degree. C. and a shear rate of 20 sec-.sup.1. In some
embodiments, the viscosity of the liquid may be in the range of
from about 200 to about 1000 mPa*s at 25.degree. C. at a shear rate
of 20 sec-.sup.1. In some embodiments, the viscosity of the liquid
may be in the range of from about 200 to about 500 mPa*s at
25.degree. C. at a shear rate of 20 sec-.sup.1.
All temperatures herein are in degrees Celsius (.degree. C.) unless
otherwise indicated. Unless otherwise specified, all measurements
herein are conducted at 25.degree. C. and under the atmospheric
pressure.
As used herein the phrase "detergent composition," "cleaning
composition" or "detergent or cleaning composition" includes
compositions and formulations designed for cleaning soiled
material. Such compositions include but are not limited to, laundry
detergent compositions, fabric softening compositions, fabric
enhancing compositions, fabric freshening compositions, laundry
prewash, laundry pretreat, laundry additives, spray products, dry
cleaning agent or composition, laundry rinse additive, wash
additive, post-rinse fabric treatment, ironing aid, dish washing
compositions, hard surface cleaning compositions, unit dose
formulation, delayed delivery formulation, detergent contained on
or in a porous substrate or nonwoven sheet, and other suitable
forms that may be apparent to one skilled in the art in view of the
teachings herein. Such compositions may be used as a pre-cleaning
treatment, a post-cleaning treatment, or may be added during the
rinse or wash cycle of the cleaning process. The cleaning
compositions may have a form selected from liquid, powder,
single-phase or multi-phase unit dose or pouch form (e.g., a liquid
detergent composition that is contained in a single compartment or
multi-compartment water-soluble pouch, e.g., formed by a
water-soluble polymer such as poly-vinyl alcohol (PVA) or
copolymers thereof), tablet, gel, paste, bar, or flake. In a
preferred embodiment of the present invention, the detergent or
cleaning composition of the present invention is a liquid laundry
or dish detergent composition, which is designated for either
hand-washing or machine-washing of fabric or dishes. More
preferably, the detergent or cleaning composition of the present
invention is a liquid laundry or dish detergent composition
designated for hand-washing purposes.
As used herein, "suds" indicates a non-equilibrium dispersion of
gas bubbles in a relatively smaller volume of a liquid. The terms
like "suds", "foam" and "lather" can be used interchangeably within
the meaning of the present invention.
As used herein, "sudsing profile" refers to the properties of a
cleaning composition relating to suds character during the wash
and/or rinse cycles. The sudsing profile of a cleaning composition
includes, but is not limited to, the speed of suds generation upon
dissolution in the wash liquor, the volume and retention of suds in
the wash cycle, and the volume and disappearance of suds in the
rinse cycle.
Unless otherwise specified, the term "molecular weight" as used
herein refers to the weight average molecular weight (MWw) of the
polymer chains in a polymer composition, which may be calculated
using the equation: MWw=(.SIGMA.i Ni Mi.sup.2)/(.SIGMA.i Ni Mi)
wherein Ni is the number of molecules having a molecular weight
Mi.
The term "average number-average molecular weight (MWn)" as used
herein is calculated using the equation: MWn=(.SIGMA.i Ni
Mi)/(.SIGMA.i Ni) wherein Ni is the number of molecules having a
molecular weight Mi.
As used herein "mol %" refers to the relative molar percentage of a
particular monomeric structural unit in a polymer. It is understood
that within the meaning of the present invention, the relative
molar percentages of all monomeric structural units that are
present in the cationic polymer shall add up to 100 mol %.
As used herein, term "substituted" is defined herein as
encompassing moieties or units which can replace a hydrogen atom,
two hydrogen atoms, or three hydrogen atoms of a hydrocarbyl
moiety, inter alia, aromatic ring, alkyl chain, and the like. When
a moiety is described a "substituted" any number of the hydrogen
atoms may be replaced. For example, a substituted unit that
requires a single hydrogen atom replacement includes halogen,
hydroxyl, and the like. A two hydrogen atom replacement includes
carbonyl, oximino, and the like. A two hydrogen atom replacement
from adjacent carbon atoms includes epoxy, and the like. A three
hydrogen replacement includes cyano, and the like. An epoxide unit
is an example of a substituted unit which requires replacement of a
hydrogen atom on adjacent carbons. Also substituted can include
replacement of hydrogen atoms on two adjacent carbons to form a new
moiety or unit.
Unless otherwise specified, the term "alkyl" as used herein means a
C.sub.1-C.sub.10 hydrocarbyl moiety which can be linear or
branched, substituted or unsubstituted.
As used herein, the term "hydrocarbyl" is defined herein as any
organic unit or moiety which is comprised of carbon atoms and
hydrogen atoms. Included with the definition of "hydrocarbyl" are
the aromatic (aryl) and non-aromatic carbocyclic rings. Further
included within the term hydrocarbyl are heterocycles. The term
"heterocycle" includes both aromatic (heteroaryl) and non-aromatic
heterocyclic rings.
In all embodiments of the present invention, all percentages are by
weight of the total composition, unless specifically stated
otherwise. All ratios are weight ratios, unless specifically stated
otherwise. The dimensions and values disclosed herein are not to be
understood as being strictly limited to the exact numerical values
recited. Instead, unless otherwise specified, each such dimension
is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm."
It is understood that the test methods that are disclosed in the
Test Methods Section of the present application must be used to
determine the respective values of the parameters of Applicants'
inventions are described and claimed herein.
Alkoxylated Polyalkyleneimine
The cleaning composition of the present invention contains at least
one, and preferably two or more, alkoxylated polyalkyleneimine.
The alkoxylated polyalkylenimines of the present invention may be
represented as containing repeating units of formulae (1), (2), (3)
and (4)
##STR00001## wherein: # in each case denotes one-half of a bond
between a nitrogen atom and the free binding position of a group
A.sup.1 of two adjacent repeating units of formulae (1), (2), (3)
or (4); A.sup.1 is independently selected from linear or branched
C.sub.2-C.sub.6 alkylene; E is independently selected from
alkylenoxy units of the formula (5):
##STR00002## wherein: * in each case denotes the bond to the
nitrogen atom of the repeating unit of formula (1), (2) or (4);
A.sup.2 is in each case independently selected from 1,2-propylene,
1,2-butylene and 1,2-isobutylene; R is in each case independently
selected from hydrogen and C.sub.1-C.sub.4-alkyl; m has an average
value in the range of from 0 to about 2; n has an average value in
the range of from about 20 to about 50; and p is a rational number
from about 10 to about 50; the individual alkoxylated
polyalkylenimines consisting of 1 repeating unit of formula (1), x
repeating units of formula (2), y repeating units of formula (3)
and y+1 repeating units of formula (4), wherein x and y in each
case have a value in the range of from 0 to about 150; and the
polymer has a degree of quaternization of from 0 to about 50%. For
more information regarding the alkoxylated polyalkyleneimines,
please see U.S. Pat. No. 8,097,579B and WO2006/108856A1.
In a simplified representation, the alkoxylated polyalkyleneimines
of the present invention can be considered as having a
polyalkyleneimine core and at least one side chain bonded to a
nitrogen atom in the polyalkyleneimine core.
The polyalkyleneimine core is formed by the repeating units of
formulae (1), (2), (3) and (4) as described hereinabove, but minus
the alkylenoxy units E. The polyalkyleneimine core of the
alkoxylated polyalkyleneimine of the present invention has an
average number-average molecular weight (MWn) ranging from about
100 to about 100,000 Daltons, preferably from about 100 to about
5000 Daltons, and more preferably from about 200 to about 1000
Daltons.
The at least one side chain of the alkoxylated polyalkyleneimine,
which is formed by the alkylenoxy units E as described hereinabove,
preferably has an inner polyethylene oxide block and an outer
polypropylene oxide block, which can be represented by an empirical
formula (I) of: -(EO).sub.b(PO).sub.c--R (I) while EO is ethylene
oxide; b has a weight average value ranging from about 3 to about
60; PO is propylene oxide; c has a weight average value ranging
from 0 to about 60; R is selected from the group consisting of
hydrogen, C.sub.1-C.sub.4 alkyls, and combinations thereof.
In a preferred embodiment of the present invention, the cleaning
composition contains a first alkoxylated polyalkyleneimine having a
polyalkyleneimine core with Mwn ranging from about 100 to about
5000 Daltons, and preferably from about 200 to about 1000 Daltons;
b ranges from about 10 to about 50, preferably from about 15 to
about 40, more preferably from about 20 to about 30; and wherein c
ranges from about 1 to about 50, preferably from about 5 to about
40, and more preferably from about 10 to about 30. Said first
alkoxylated polyalkyleneimine can be represented by an empirical
formula of (PEI).sub.200-1000(EO).sub.20-30(PO).sub.10-30.
Preferably but not necessarily, the cleaning composition may
further contain a second alkoxylated polyalkyleneimine having a
polyalkyleneimine core with Mwn ranging from about 100 to about
5000 Daltons, and preferably from about 200 to about 1000 Daltons;
b ranges from about 5 to about 40, preferably from about 10 to
about 30, more preferably from about 15 to 25; and wherein c is 0.
Said second alkoxylated polyalkyleneimine can be represented by an
empirical formula of (PEI).sub.200-1000(EO).sub.15-25. The weight
ratio between such first and second alkoxylated polyalkyleneimines
may range from about 1:10 to about 10:1, preferably from about 1:5
to about 5:1, and more preferably from about 1:2 to about 2:1.
The above-described alkoxylated polyalkyleneimine(s) may be present
in the cleaning composition of the present invention in an amount
ranging from about 0.01 wt % to about 20 wt %, preferably from
about 0.05 wt % to about 15 wt %, more preferably from about 0.1 wt
% to about 10 wt %, and most preferably from about 0.5 wt % to
about 5 wt %. In a particularly preferred embodiment of the present
invention, the cleaning composition contains from about 0.1 wt % to
about 5 wt % of the first alkoxylated polyalkyleneimine, and from 0
wt % to about 2 wt % of the second alkoxylated
polyalkyleneimine.
Organomodified Silicone Comprising Aryl Moieties
The cleaning composition of the present invention further contains
an organomodified silicone comprising one or more aryl moieties
each comprising a 5- to 9-membered aromatic ring. Such an aromatic
ring can be either substituted or unsubstituted, either
heteroatomic or homoatomic, either monocyclic or multicyclic. For
example, the aromatic ring can be selected from the group
consisting of phenyl, furan, pyrrole, thiophene, imidazole,
pyrazole, oxazole, pyridine, pyrazine, naphthalene, anthracene
moieties, and derivatives thereof. Preferably, the aromatic ring is
substituted with at least one aliphatic group. In a particularly
preferred embodiment of the present invention, such one or more
aryl moieties are selected from alkylphenyl moieties, and more
preferably such one or more aryl moieties are 2-phenylpropyl
moieties, which is also commonly referred to as alpha-methylstyrene
moieties.
The organomodified silicone may further comprise one or more
C.sub.2-C.sub.20 aliphatic moieties, and preferably one or more
C.sub.6-C.sub.10 alkyl moieties, which can be either substituted or
unsubstituted, either heteroatomic or homoatomic.
Said organomodified silicone may comprise units of the following
formula (II):
R.sub.a(R.sup.1O).sub.bR.sup.2.sub.cSiO.sub.(4-a-b-c)/2 (II)
wherein: a) each R is independently selected from the group
consisting of: H; the aryl moieties as described hereinabove, which
contain a substituted aromatic ring with at least one aliphatic
group and is covalently attached to a silicon atom of the
organomodified silicone via the aliphatic groups; and a monovalent,
SiC-bonded aliphatic hydrocarbon radical, which is optionally
substituted and optionally comprises a heteroatom; b) each R.sup.1
is independently selected from the group consisting of: H; and a
monovalent aliphatic hydrocarbon radical, which is optionally
substituted and optionally comprises a heteroatom; c) each R.sup.2
is independently selected from the group consisting of: H; the aryl
moieties as described hereinabove, which contain a substituted
aromatic ring with at least one aliphatic group and is covalently
attached to a silicon atom of the organomodified silicone via the
aliphatic groups; the aryl moieties as described hereinabove, which
contain a substituted artomic ring and is covalently attached to a
silicon atom of the organomodified silicone via a carbon ring atom;
and a monovalent, SiC-bonded aliphatic hydrocarbon radical, which
is optionally substituted and optionally comprises a heteroatom; d)
the index a is 0, 1, 2 or 3; e) the index b is 0, 1, 2 or 3; and f)
the index c is 0, 1, 2 or 3.
The sum of a+b+c is typically less than or equal to 3, and it is
preferably an average of from about 1.5 to about 2.4, more
preferably an average of from about 1.8 to about 2.3, and most
preferably from about 1.9 to about 2.1. The organomodified silicone
may comprise from about 5 to about 10,000, preferably from about 10
to about 5,000, and more preferably from about 50 to about 1,000,
and most preferably from about 100 to about 500, siloxane units of
formula (I).
In a preferred embodiment of the present invention, the
organomodified silicone comprises a sufficient number of R and
R.sup.2 moieties that comprise the preferred aryl moieties to
provide from about 1 mol % to about 75 mol % of siloxane units with
2-phenylpropyl moieties attached thereto and from about 1 mol % to
about 20 mol % of siloxane units with C.sub.6-C.sub.10 alkyl
moieties attached thereto, provided that none of the 2-phenylpropyl
moieties and none of the C.sub.6-C.sub.10 alkyl moieties are
attached to the same silicon atom. More preferably, the
organomodified silicone contains from about 5 mol % to about 50 mol
% or from about 10 mol % to about 40 mol % of siloxane units with
2-phenylpropyl moieties attached thereto, and from about 2 mol % to
about 15 mol % or from about 3 mol % to about 10 mol % of siloxane
units with C.sub.6-C.sub.10 alkyl moieties attached thereto. Most
preferably, the organomodified silicone contains from about 15 mol
% to about 25 mol % of the 2-phenylpropyl moieties and from about 4
mol % to about 8 mol % of C.sub.6-C.sub.10 alkyl moieties. Please
note that the total mol % of all siloxane units, either substituted
or unsubstituted, in the organomodified silicone adds to 100 mol
%.
The weight average molecular weight (MWw) of the organomodified
silicone of the present invention may range from about 1,000 to
about 500,000, preferably from about 5,000 to about 200,000, more
preferably from about 10,000 to about 150,000, and most preferably
from about 50,000 to about 100,000, Daltons. The number average
molecular weight of the organomodified silicone of the present
invention may range from about 1,000 to about 500,000, preferably
from about 2,000 to about 200,000, more preferably from about 5,000
to about 100,000, and most preferably from about 10,000 to about
50,000, Daltons.
The organomodified silicone can be present in the cleaning
composition of the present invention in an amount ranging from
about 0.001 wt % to about 10 wt %, preferably from about 0.005 wt %
to about 5 wt %, more preferably from about 0.01 wt % to about 2 wt
%, and most preferably from about 0.02 wt % to about 0.5 wt %.
Siloxane-Based Diluent
The cleaning composition of the present invention further contains
a siloxane-based diluent that is characterized by a Solubility
Index (calculated according to the Solubility Index Test described
hereinafter) of from about 0.8 to about 1.25 in the above-described
organomodified silicone. Preferably, the siloxane-based diluent is
characterized by a Solubility Index of from about 0.85 to about
1.2, more preferably from about 0.9 to about 1.1, and most
preferably from about 0.95 to about 1.0.
In a preferred but not necessary embodiment of the present
invention, the siloxane-based diluent contains one or more
polydimethylsiloxanes (PDMS) having viscosity ranging from about
0.5 cSt to about 10,000 cSt, preferably from about 1 cSt to about
1,000 cSt, more preferably from about 2 cSt to about 100 cSt, and
most preferably from about 5 cSt to about 15 cSt, measured at a
shear rate of 20 sec.sup.-1 and 25.degree. C. The PDMS can be
linear, branched, cyclic, grafted or cross-linked or cyclic
structures, while linear PDMS is particularly preferred.
The siloxane-based diluent can be present in the cleaning
composition of the present invention in an amount ranging from
about 0.001 wt % to about 10 wt %, preferably from about 0.002 wt %
to about 5 wt %, more preferably from about 0.01 wt % to about 2 wt
%, and most preferably from about 0.02 wt % to about 0.5 wt %.
In a particularly preferred embodiment of the present invention,
the siloxane-based diluent may contain a combination of two or more
PDMSs of different viscosity. For example, the siloxane-based
diluent may include a first polydimethylsiloxane having a first,
higher viscosity of from about 8 cSt to about 12 cSt and a second
polydimethylsiloxane having a second, lower viscosity of from about
5 cSt to about 10 cSt, when measured at a shear rate of about 20
sec.sup.-1 and about 25.degree. C. Specifically, it is preferred
that the first PDMS is present in an amount ranging from about
0.001 wt % to about 10 wt %, preferably from about 0.002 wt % to
about 2.5 wt %, more preferably from about 0.01 wt % to about 1 wt
%, and most preferably from about 0.02 wt % to about 0.25 wt % by
total weight of the detergent or cleaning composition; and the
second polydimethylsiloxane is present in an amount ranging from 0%
to about 10 wt %, preferably from about 0.002 wt % to about 2.5 wt
%, more preferably from about 0.01 wt % to about 1 wt %, and most
preferably from about 0.02 wt % to about 0.25 wt % by total weight
of the cleaning composition. More preferably, the weight ratio of
the first PDMS over the second PDMS is preferably greater than
about 1:1.
Hydrophobic Silica
In a preferred but not necessary embodiment of the present
invention, the cleaning composition further comprises
hydrophobically modified silica particles. Such hydrophobically
modified silica particles may have: (1) a surface area as measured
by BET measurement of from about 50 m.sup.2/g to about 800
m.sup.2/g, preferably from about 80 to about 200 m.sup.2/g; and (2)
an average particle size ranging from about 0.5 to about 50
microns, preferably from about 1 to about 40 microns, more
preferably from about 2 to about 30 microns, and most preferably
from about 5 to about 25 microns.
Silica particles are typically not hydrophobic in nature, so the
hydrophobically modified silica particles are formed by surface
treatment of silica particles with a hydrophobing agent. The silica
particles are preferably those prepared by heating, e.g., fumed
silica, or by precipitation, or by a sol-gel process, while
precipitated silica particles are particularly preferred. Suitable
hydrophobing agents include, but are not limited to: methyl
substituted organosilicone materials, fatty acids,
polydimethylsiloxanes, dimethylsiloxane polymers that are
end-blocked with silanol or silicon-bonded alkoxy groups,
hexamethyldisilazane, hexamethyldisiloxane, and organosilicone
resins. Hydrophobing of the silica particles are typically carried
out at a temperature of at least 80.degree. C. Commercially
available hydrophobic silica particles include those sold under the
trade names Sipernat.RTM.D10 or Sipernat.RTM.D13 from Degussa AG,
Germany.
The hydrophobic silica can be present in the detergent or cleaning
composition of the present invention in an amount ranging from
about 0.0001 wt % to about 1 wt %, preferably from about 0.0004 wt
% to about 0.5 wt %, more preferably from about 0.001 wt % to about
0.15 wt %, and most preferably from about 0.002 wt % to about 0.05
wt %.
Silicone Resin
Preferably but not necessarily, the cleaning composition of the
present invention may further comprise a silicone resin. The
silicone resin may comprise units of formula (III) below:
R.sup.3.sub.d(R.sup.4O).sub.eSiO.sub.(4-d-e)/2 (III) wherein: a)
each R.sup.3 is independently selected from the group consisting
of: H; a monovalent, SiC-bonded, aliphatic hydrocarbon radical that
is optionally substituted and optionally comprises a heteroatom;
and an aromatic hydrocarbon radical that is covalently attached to
a silicon atom of the silicone resin via aliphatic groups; b) each
R.sup.4 is independently selected from the group consisting of: H;
a monovalent aliphatic hydrocarbon radical that is optionally
substituted and optionally comprises a heteroatom; c) the index d
is 0, 1, 2 or 3; and d) the index e is 0, 1, 2 or 3.
The sum of d+e is typically less than or equal to 3, and preferably
less than about 30% or more preferably less than about 5% of all
siloxane units of formula (III) in the silicone resin have the sum
of d+e=2.
More preferably, the value of d is either 3 or 0. In this manner,
the silicone resin of the present invention is composed essentially
of R.sup.3.sub.3SiO.sub.1/2 (M) units and SiO.sub.4/2 (Q) units,
while R.sup.3 is as defined hereinabove. Such resins are typically
referred to as MQ resins. The molar ratio of M units to Q units is
preferably from about 0.5 to about 2.0, more preferably from about
0.6 to about 1.0. These MQ resins may also contain up to about 10%
by weight of hydroxyl or alkoxy groups. Although it is preferred
that the MQ resins are solid at room temperature, liquid MQ resins
having a M/Q ratio of about 1.2 or higher can also be used
successfully.
The silicone resin of the present invention is preferably provided
as a solution containing a non-volatile solvent. Suitable
non-volatile solvents include various oils, alcohols, and esters of
carboxylic acids, such as fatty acid esters. Preferred solvents
include esters of carboxylic acids, such as dioctyl phthalate,
diethyl succinate, methyl caproate, butyl perlargonate, ethyl
stearate, 2-ethylhexyl stearate, dodecyl laurate, methyl melissate,
and the like.
For more details regarding the organomodified silicone, the
siloxane-based diluent, the hydrophobically modified silica, the
silicone resin, and the solvent, please see US2011/0209291, U.S.
Pat. No. 7,566,750, and U.S. Pat. No. 8,536,109.
The silicone resin can be present in the cleaning composition of
the present invention in an amount ranging from about 0.0001 wt %
to about 1 wt %, preferably from about 0.0002 wt % to about 0.5 wt
%, more preferably from about 0.001 wt % to about 0.1 wt %, and
most preferably from about 0.002 wt % to about 0.05 wt %.
Solvent for the Silicone Resin
Preferably but not necessarily, the cleaning composition of the
present invention may further comprise a solvent for the silicone
resin. Suitable emulsifiers are non-volatile organic solvents,
including alcohols such as dodecanol, 2-butyl-octanol and the like,
or fatty acid esters such as octyl stearate, 2-ethylhexyl stearate
and the like. A particularly preferred solvent is 2-ethylhexyl
stearate.
The solvent can be present in the cleaning composition of the
present invention in an amount ranging from 0 wt % to about 0.5 wt
%, preferably from about 0.0002 wt % to about 0.2 wt %, more
preferably from about 0.001 wt % to about 0.1 wt %, and most
preferably from about 0.002 wt % to about 0.05 wt %.
Cleaning Compositions
The cleaning composition of the present invention can be personal
care cleaners, such as those used in the health and beauty areas,
including shampoos and soaps, which may benefit from products
having improved rinse suds profiles. In another aspect, the
cleaning composition is suitable for cleaning various hard
surfaces, such as hard wood, tile, ceramic, plastic, leather,
metal, glass, etc. The cleaning composition is also suitable to be
used for dish washing, either as automatic machine dishwashing
detergents or as hand-washing dish detergents. Further, the
cleaning composition of the present invention is suitable for
fabric cleaning application, including automatic machine washing or
hand-washing of fabrics, or cleaning auxiliaries, such as for
example, bleach, rinse aids, additives or pre-treat types.
The cleaning compositions can be in any form, namely, in the form
of a liquid; a solid such as a powder, granules, agglomerate,
paste, tablet, pouches, bar, gel; an emulsion; types delivered in
dual- or multi-compartment containers or pouches; a spray or foam
detergent; premoistened wipes (i.e., the cleaning composition in
combination with a nonwoven material); dry wipes (i.e., the
cleaning composition in combination with a nonwoven materials)
activated with water by a consumer; and other homogeneous or
multiphase consumer cleaning product forms.
The cleaning composition is preferably a liquid laundry or dish
detergent and can be a fully formulated laundry or dish detergent
product. Liquid compositions contained in encapsulated and/or
unitized dose products are included, as are compositions which
comprise two or more separate but jointly dispensable portions.
More preferably, the liquid detergent composition is a liquid
laundry or dish detergent composition designed for hand-washing,
where the improved suds benefit or superior sudsing profile is most
evident to the consumer. The liquid laundry or dish detergent
composition preferably contains water as an aqueous carrier, and it
can contain either water alone or mixtures of organic solvent(s)
with water as carrier(s). Suitable organic solvents are linear or
branched lower C.sub.1-C.sub.8 alcohols, diols, glycerols or
glycols; lower amine solvents such as C.sub.1-C.sub.4
alkanolamines, and mixtures thereof. Exemplary organic solvents
include 1,2-propanediol, ethanol, glycerol, monoethanolamine and
triethanolamine. The carriers are typically present in a liquid
composition at levels in the range of from about 0.1% to about 98%,
preferably from about 10% to about 95%, more preferably from about
25% to about 75% by total weight of the liquid composition. In some
embodiments, water is from about 85 to about 100 wt % of the
carrier. In other embodiments, water is absent and the composition
is anhydrous. Highly preferred compositions afforded by the present
invention are clear, isotropic liquids.
The liquid detergent composition of the present invention has a
viscosity from about 1 to about 2000 centipoise (1-2000 mPas), or
from about 200 to about 800 centipoises (200-800 mPas). The
viscosity can be determined using a Brookfield viscometer, No. 2
spindle, at 60 RPM/s, measured at 25.degree. C.
In addition to the ingredients described hereinabove, the cleaning
compositions of the present invention may comprise one or more
surfactants at amounts ranging from about 1% to about 80%, more
preferably from about 1% to about 50%, and more preferably from
about 5% to about 30% by total weight of the compositions.
Detersive surfactants utilized can be of the anionic, nonionic,
zwitterionic, amphoteric or cationic type or can comprise
compatible mixtures of these types.
Anionic surfactants are preferred. Useful anionic surfactants can
themselves be of several different types. For example, non-soap
synthetic anionic surfactants are particularly suitable for use
herein, which include the water-soluble salts, preferably the
alkali metal, and ammonium salts, of organic sulfuric reaction
products having in their molecular structure an alkyl group
(included in the term "alkyl" is the alkyl portion of acyl groups)
containing from about 10 to about 20 carbon atoms and a sulfonic
acid or sulfuric acid ester group. Examples of this group of
synthetic anionic surfactants include, but are not limited to: a)
the sodium, potassium and ammonium alkyl sulfates with either
linear or branched carbon chains, especially those obtained by
sulfating the higher alcohols (C.sub.10-C.sub.20 carbon atoms),
such as those produced by reducing the glycerides of tallow or
coconut oil; b) the sodium, potassium and ammonium alkylethoxy
sulfates with either linear or branched carbon chains, particularly
those in which the alkyl group contains from about 10 to about 20,
preferably from about 12 to about 18 carbon atoms, and wherein the
ethoxylated chain has, in average, a degree of ethoxylation ranging
from about 0.1 to about 5, preferably from about 0.3 to about 4,
and more preferably from about 0.5 to about 3; c) the sodium and
potassium alkyl benzene sulfonates in which the alkyl group
contains from about 10 to about 20 carbon atoms in either a linear
or a branched carbon chain configuration, preferably a linear
carbon chain configuration; d) the sodium, potassium and ammonium
alkyl sulphonates in which the alkyl group contains from about 10
to about 20 carbon atoms in either a linear or a branched
configuration; e) the sodium, potassium and ammonium alkyl
phosphates or phosphonates in which the alkyl group contains from
about 10 to about 20 carbon atoms in either a linear or a branched
configuration, f) the sodium, potassium and ammonium alkyl
carboxylates in which the alkyl group contains from about 10 to
about 20 carbon atoms in either a linear or a branched
configuration, and combinations thereof; g) the sodium, potassium
and ammonium alkyl ester sulfonates, for example of formula
R--CH(SO.sub.3M)-CH.sub.2COOR', or the sodium, potassium and
ammonium alkyl ester sulfates, for example of formula
R--CH(OSO.sub.3M)--CH.sub.2COOR', where R represents a
C.sub.10-C.sub.20 and preferably C.sub.10-C.sub.16 linear or
branched alkyl radical, R' represents a C.sub.1-C.sub.6 and
preferably C.sub.1-C.sub.3 alkyl radical, and M represents a
sodium, potassium or the ammonium cation.
Especially preferred for the practice of the present invention are
anionic surfactant systems containing C.sub.10-C.sub.20 linear
alkyl benzene sulphonates, C.sub.10-C.sub.20 linear or branched
alkylethoxy sulfates having an average degree of ethoxylation
ranging from about 0.1 to about 5 (preferably from about 0.3 to
about 4 and more preferably from about 0.5 to about 3, which is
particularly advantageous for improving the sudsing profile of the
detergent composition), or mixtures thereof. The anionic
surfactants can be provided in the cleaning compositions of the
present invention at levels ranging from about 1% to about 80%,
more preferably from about 1% to about 50%, and more preferably
from about 5% to about 30% by total weight of the compositions.
In one particularly preferred embodiment, the cleaning composition
of the present invention is a liquid laundry or dish detergent
composition containing from about 1 wt % to about 50 wt % of one or
more anionic surfactants selected from the group consisting of
C.sub.10-C.sub.20 linear alkyl benzene sulphonates,
C.sub.10-C.sub.20 linear or branched alkylethoxy sulfates having an
average degree of ethoxylation ranging from 0.1 to 5.0,
C.sub.10-C.sub.20 linear or branched alkyl sulfates,
C.sub.10-C.sub.20 linear or branched alkyl ester sulfates,
C.sub.10-C.sub.20 linear or branched alkyl sulphonates,
C.sub.10-C.sub.20 linear or branched alkyl ester sulphonates,
C.sub.10-C.sub.20 linear or branched alkyl phosphates,
C.sub.10-C.sub.20 linear or branched alkyl phosphonates,
C.sub.10-C.sub.20 linear or branched alkyl carboxylates, and
combinations thereof. More preferably, said one or more anionic
surfactants are selected from the group consisting of
C.sub.10-C.sub.20 linear alkyl benzene sulphonates,
C.sub.10-C.sub.20 linear or branched alkylethoxy sulfates having an
average degree of ethoxylation ranging from about 0.5 to about 3,
methyl ester sulfonates with a C.sub.10-C.sub.20 linear or branched
alkyl group, and combinations thereof, and are present in an amount
ranging from about 5 wt % to about 30 wt % of the liquid laundry or
dish detergent composition.
Water-soluble salts of the higher fatty acids, i.e., "soaps", are
also useful anionic surfactants in the cleaning compositions of the
present invention. This includes alkali metal soaps such as the
sodium, potassium, ammonium, and alkyl ammonium salts of higher
fatty acids containing from about 8 to about 24 carbon atoms, and
preferably from about 12 to about 18 carbon atoms. Soaps can be
made by direct saponification of fats and oils or by the
neutralization of free fatty acids. Particularly useful are the
sodium and potassium salts of the mixtures of fatty acids derived
from coconut oil and tallow, i.e., sodium or potassium tallow and
coconut soap. However, the cleaning compositions of the present
invention preferably contains soaps at a relatively low level,
e.g., no more than about 3 wt %, more preferably not more than
about 2 wt % or 1 wt %, and most preferably said cleaning
composition is essentially free of soaps.
Nonionic surfactants can also be included into the surfactant
systems of the present invention, which include those of the
formula R.sup.1(OC.sub.2H.sub.4).sub.nOH, wherein R.sup.1 is a
C.sub.8-C.sub.18 alkyl group or alkyl phenyl group, and n is from
about 1 to about 80. Particularly preferred are C.sub.8-C.sub.18
alkyl alkoxylated alcohols having an average degree of alkoxylation
from about 1 to about 20. The nonionic surfactants can be provided
in the cleaning compositions at levels ranging from about 0.05 wt %
to about 20 wt %, preferably from about 0.1 wt % to about 10 wt %,
and most preferably from about 1 wt % to about 5 wt %. However, in
certain preferred embodiments of the present invention, the
cleaning compositions contains nonionic surfactants at a relatively
low level, e.g., no more than about 3 wt %, more preferably not
more than about 2 wt % or 1 wt %, and most preferably said cleaning
composition is essentially free of nonionic surfactants.
Other surfactants useful herein include amphoteric surfactants,
zwitterionic surfactants and cationic surfactants. Such surfactants
are well known for use in laundry or dish detergents and are
typically present at levels from about 0.2 wt %, 0.5 wt % or 1 wt %
to about 10 wt %, 20 wt % or 30 wt %.
In a preferred but not necessary embodiment of the present
invention, the cleaning composition is a liquid dish detergent
composition containing from about 0.5 wt % to about 20 wt % of one
or more amphoteric and/or zwitterionic surfactants.
Preferred amphoteric surfactants are selected from the group
consisting of amine oxide surfactants, such as, for example, alkyl
dimethyl amine oxide or alkyl amido propyl dimethyl amine oxide,
more preferably alkyl dimethyl amine oxide and especially coco
dimethyl amino oxide. Amine oxide may have a linear or mid-branched
alkyl moiety. Typical linear amine oxides are characterized by a
formula R.sub.1--N(R.sub.2)(R.sub.3)--O, wherein R.sub.1 is a
C.sub.8-18 alkyl, and wherein R.sub.2 and R.sub.3 are independently
selected from the group consisting of C.sub.1-3 alkyls and
C.sub.1-3 hydroxyalkyls, such as methyl, ethyl, propyl, isopropyl,
2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl. As used herein
"mid-branched" means that the amine oxide has one alkyl moiety
having n1 carbon atoms with one alkyl branch on the alkyl moiety
having n2 carbon atoms. The alkyl branch is located on the .alpha.
carbon from the nitrogen on the alkyl moiety. This type of
branching for the amine oxide is also known in the art as an
internal amine oxide. The total sum of n1 and n2 is from about 10
to about 24 carbon atoms, preferably from about 12 to about 20, and
more preferably from about 10 to about 16. The number of carbon
atoms for the one alkyl moiety (n1) should be approximately the
same number of carbon atoms as the one alkyl branch (n2) such that
the one alkyl moiety and the one alkyl branch are symmetric. As
used herein "symmetric" means that |n1-n2| is less than or equal to
5, preferably 4, most preferably from 0 to 4 carbon atoms in at
least about 50 wt %, more preferably at least about 75 wt % to
about 100 wt %, of the mid-branched amine oxides for use herein.
Particularly preferred amphoteric surfactants are C.sub.10-C.sub.14
alkyl dimethyl amine oxides.
Preferred zwitterionic surfactants are betaine surfactants, such
as, for example, alkyl betaines, alkylamidobetaines,
amidazoliniumbetaines, sulfobetaines (also referred to as
sultaines) as well as phosphobetaines. A particularly preferred
betaine is cocoamidopropylbetaine.
The liquid detergent composition as described herein above may also
contain an external structurant, which may be present in an amount
ranging from about 0.001% to about 1.0%, preferably from about
0.05% to about 0.5%, more preferably from about 0.1% to about 0.3%
by total weight of the composition. Suitable external structurants
include those described, for example, in US2007/169741 and
US2005/0203213. A particularly preferred external structurant for
the practice of the present invention is hydrogenated castor oil,
which is also referred to as trihydroxylstearin and is commercially
available under the tradename Thixin.RTM..
In yet another preferred embodiment of the present invention, the
liquid detergent composition further contains from about 0.1 wt %
to about 5 wt %, preferably from about 0.5 wt % to about 3 wt %,
more preferably from about 1 wt % to about 1.5 wt %, of one or more
fatty acids and/or alkali salts thereof. Suitable fatty acids
and/or salts that can be used in the present invention include
C.sub.10-C.sub.22 fatty acids or alkali salts thereof. Such alkali
salts include monovalent or divalent alkali metal salts like
sodium, potassium, lithium and/or magnesium salts as well as the
ammonium and/or alkylammonium salts of fatty acids, preferably the
sodium salt.
The balance of the cleaning composition of the present invention
typically contains from about 5 wt % to about 70 wt %, or about 10
wt % to about 60 wt % adjunct ingredients.
Suitable adjunct ingredients for laundry detergent products
include: builders, chelating agents, dye transfer inhibiting
agents, dispersants, rheology modifiers, enzymes, and enzyme
stabilizers, catalytic materials, bleach activators, hydrogen
peroxide, sources of hydrogen peroxide, preformed peracids,
polymeric dispersing agents, clay soil removal/anti-redeposition
agents, brighteners, suds suppressors, dyes, photobleaches,
structure elasticizing agents, fabric softeners, carriers,
hydrotropes, processing aids, solvents, hueing agents,
anti-microbial agents, free perfume oils, and/or pigments. In
addition to the disclosure below, suitable examples of such other
adjunct ingredients and levels of use are found in U.S. Pat. Nos.
5,576,282, 6,306,812, and 6,326,348. The precise nature of these
adjunct ingredients and the levels thereof in the liquid laundry
detergent composition will depend on factors like the specific type
of the composition and the nature of the cleaning operation for
which it is to be used.
Suitable adjunct ingredients for dish detergent products include:
builders, chelants, conditioning polymers, cleaning polymers,
surface modifying polymers, soil flocculating polymers,
structurants, emmolients, humectants, skin rejuvenating actives,
enzymes, carboxylic acids, scrubbing particles, bleach and bleach
activators, perfumes, malodor control agents, pigments, dyes,
opacifiers, beads, pearlescent particles, microcapsules, organic
and inorganic cations such as alkaline earth metals such as
Ca/Mg-ions and diamines, antibacterial agents, preservatives and pH
adjusters and buffering means.
If the cleaning composition of the present invention is provided in
a powder form, it may also be especially preferred for the powder
to comprise low levels, or even be essentially free, of builder.
The term "essentially free" means that the composition "comprises
no deliberately added" amount of that ingredient. In a preferred
embodiment, the cleaning composition of the present invention
comprises no builder.
Method of Making the Cleaning Composition
Incorporation of the above-described components and various other
ingredients as described hereinabove into the cleaning compositions
of the invention can be done in any suitable manner and can, in
general, involve any order of mixing or addition.
For example, the alkoxylated polyalkyleneimine(s), the
organomodified silicone, the siloxane-based diluent, the
hydrophobically modified silica, the silicone resin and the solvent
as received from the manufacturer can be mixed first with a
surfactant, such as an alkylalkoxy sulfate and preferably an
alkylethoxy sulfate having a weight average degree of ethoxylation
ranging from about 0.1 to about 5.0, to form a foam control or
antifoam composition, which is then mixed with two or more of the
other components to form the final detergent or cleaning
composition. In another example, the alkoxylated
polyalkyleneimine(s), the organomodified silicone, the
siloxane-based diluent, the hydrophobically modified silica, the
silicone resin, and the solvent can be simultaneously mixed with
two or more of the other components to form the final cleaning
composition in one mixing step. In yet another example, the
alkoxylated polyalkyleneimine(s) can be premixed with an
emulsifier, a dispersing agent or a suspension agent to form an
emulsion, a latex, a dispersion, a suspension, and the like, which
is then mixed with a foam control composition formed by premixing
the organomodified silicone, the siloxane-based diluent, the
hydrophobically modified silica, the silicone resin, and the
solvent, followed by yet another mixing step with other components
to form the final cleaning composition. These components can be
added in any order and at any point in the process of preparing the
final composition.
Methods of Using the Cleaning Composition
The present invention in one aspect is directed to a method of
using the above-described cleaning composition to clean fabric, the
method comprising the steps of: (i) providing a cleaning
composition as described above; (ii) forming a laundry liquor by
diluting the cleaning composition with water; (iii) washing fabric
in the laundry liquor; and (iv) rinsing the fabric in water,
wherein after 2 or less rinses, preferably after 1 rinse, the
laundry liquor is substantially free of suds, or at least about
75%, preferably at least about 85%, more preferably about 95%, and
even more preferably at least about 99% of a surface area of the
laundry liquor is free from suds. The method of cleaning fabric may
be carried out in a top-loading or front-loading automatic washing
machine, or can be used in a hand-wash laundry application, which
is particularly preferred in the present invention.
The present invention in another aspect is directed to a method of
using the above-described cleaning composition to clean dishes.
Said method comprises the step of applying the cleaning
composition, preferably in liquid form, onto a dish surface, either
in diluted form or neat form, followed by rinsing. By "neat form,"
it is meant that the cleaning composition is applied directly onto
the dish surface to be treated and/or onto a cleaning device such
as a dish cloth, a sponge or brush, without undergoing any dilution
immediately prior to the application. By "diluted form," it is
meant that the cleaning composition is diluted by the user with an
appropriate solvent, typically water.
Test Methods
Various techniques are known in the art to determine the properties
of the compositions of the present invention comprising the
cationic polymer. However, the following assays must be used in
order that the invention described and claimed herein may be fully
understood.
Test 1: Solubility Index Test--Measuring the Miscibility or
Solubility of Materials in Organomodified Silicones Via UV-Vis %
Transmittance
The Solubility Index is determined by measuring the percentage of
light transmittance through samples using a UV-Vis
Spectrophotometer operated in transmission mode, at 480 nm, using 1
cm path length cuvettes, in accordance with the following
procedure. Suitable instruments include the Beckman Coulter model
DU 800 UV-Vis Spectrophotometer (Beckman Coulter Inc., Brea,
Calif., USA).
All sample preparations and analyses are conducted in a laboratory
with air temperature of 22.degree. C.+/-2.degree. C. In a glass
scintillation vial combine the predominant organocompatible
silicone present in the composition, along with the material to be
tested (for example, a polydimethyl siloxane polymer), at the ratio
of 80:20 vol/vol. Cap the vial, and mix the materials thoroughly
for 5 minutes using a benchtop vortex mixer set to its highest
speed. If two or more distinct layers of materials are clearly
visible by eye in the vial after mixing, then the Solubility Index
of the test material is considered to be indeterminate via this
method. If distinct layers are not clearly visible by eye, then
continue with the analysis.
Turn on the spectrophotometer lamps and allow them to warm up for
30 minutes prior to commencing measurements. Set the instrument to
collect the measurement in Percentage Transmission (% T) mode, at a
wavelength of 480 nm. Load all samples into 1 cm path length
plastic cuvettes. If air bubbles are visible in the cuvettes, use a
pipette to remove the bubbles, or let the bubbles settle out of the
cuvette prior to measurement.
Zero the baseline for a neat sample of the organocompatible
silicone by using a cuvette loaded with deionized (DI) water along
with a cuvette loaded with the neat silicone. Measure the % T of
the neat organocompatible silicone. Measure the % T of the mixture
of organocompatible silicone and test sample, as prepared under the
previous instructions. Compare the % T of the mixture of
organocompatible silicone and test sample, to the % T of the neat
organomodified silicone (which was measured using a DI water blank
as a baseline).
The Solubility Index is reported as a decimal number, and is
calculated as the % T of the mixture of organocompatible silicone
and test sample, divided by the % T of the neat organocompatible
silicone. For example, Solubility Index of a specific Test Sample
A=% T of ABC in Organocompatible Silicone/% T of the
Organocompatible Silicone=85%/98%=0.867
EXAMPLES
Example 1: Silicone Antifoam Agent A1
Silicone antifoam agent A1 is prepared by charging a 250 ml
container equipped with a stirrer with 71.14 g of a polymer having
a molecular weight of approximately 65,000 and comprising 71-75
mole % dimethylsiloxane groups, 20-24 mole %
2-phenylpropylmethylsiloxane groups, 3-7 mole % octylmethylsiloxane
groups and terminated with a trimethylsilyl group.sup.1, and 3.8 g
of an organosiloxane resin.sup.2 having trimethyl siloxane units
and SiO.sub.2 units in a M/Q ratio of about 0.65/1 to 0.67/1
dissolved in 20.06 g of 10 cSt. polydimethylsiloxane.sup.3. The
mixture is stirred until complete incorporation of the resin
mixture. Then 5.00 g of precipitated silica.sup.5 and is added and
the mixture stirred until complete incorporation of the silica is
achieved.
Example 2: Silicone Antifoam Agent B1
Silicone antifoam agent B1 is prepared by charging a 250 ml
container equipped with a stirrer with 69.05 g of a polymer having
a molecular weight of approximately 65,000 and comprising 71-75
mole % dimethylsiloxane groups, 20-24 mole %
2-phenylpropylmethylsiloxane groups, 3-7 octylmethylsiloxane groups
and terminated with a trimethylsilyl group.sup.1, and 2.25 g of an
organosiloxane resin.sup.2 having trimethyl siloxane units and
SiO.sub.2, units in a M/Q ratio of about 0.65/1 to 0.67/1 dissolved
in 23.70 g of 10 cSt. polydimethylsiloxane.sup.3. The mixture is
stirred until complete incorporation of the resin mixture. Then
5.00 g of precipitated silica.sup.5 and is added and the mixture
stirred until complete incorporation of the silica is achieved.
Example 3: Silicone Antifoam Agent C1
Silicone antifoam agent C1 is prepared by charging a 250 ml
container equipped with a stirrer with 67.68 g of a polymer having
a molecular weight of approximately 65,000 and comprising 71-75
mole % dimethylsiloxane groups, 20-24 mole %
2-phenylpropylmethylsiloxane groups, 3-7 mole % octylmethylsiloxane
groups and terminated with a trimethylsilyl group.sup.1, and 2.25 g
of an organosiloxane resin.sup.2 having trimethyl siloxane units
and SiO.sub.2 units in a M/Q ratio of about 0.65/1 to 0.67/1
dissolved in 22.55 g of 10 cSt. polydimethylsiloxane.sup.3. The
mixture is stirred until complete incorporation of the resin
mixture. Then 7.52 g of precipitated silica.sup.5 and is adder and
the mixture stirred until complete incorporation of the silica is
achieved.
Example 4: Silicone Antifoam Agent D1
Silicone antifoam agent D1 is prepared by charging a 250 ml
container equipped with a stirrer with 70.56 g of a polymer having
a molecular weight of approximately 65,000 and comprising 71-75
mole % dimethylsiloxane groups, 20-24 mole %
2-phenylpropylmethylsiloxane groups, 3-7 mole % octylmethylsiloxane
groups and terminated with a trimethylsilyl group.sup.1, 3.80 g of
an organosiloxane resin.sup.2 having trimethyl siloxane units and
SiO.sub.2 units in a M/Q ratio of about 0.65/1 to 0.67/1 dissolved
in 3.00 g of 2-ethylhexyl stearate.sup.4 and 17.64 g of 10 cSt.
polydimethylsiloxane.sup.3. The mixture is stirred until complete
incorporation of the resin mixture. Then 5.00 g of precipitated
silica.sup.5 led and the mixture stirred until complete
incorporation of the silica is achieved.
Example 5: Silicone Antifoam Agent E1
Silicone antifoam agent E1 is prepared by charging a 250 ml
container equipped with a stirrer with 67.68 g of a polymer having
a molecular weight of approximately 65,000 and comprising 71-75
mole % dimethylsiloxane groups, 20-24 mole %
2-phenylpropylmethylsiloxane groups, 3-7 mole % octylmethylsiloxane
groups and terminated with a trimethylsilyl group.sup.1, and 2.25 g
of an organosiloxane resin.sup.2 having trimethyl siloxane units
and SiO.sub.2 units in a M/Q ratio of about 0.65/1 to 0.67/1
dissolved in 22.55 g of 10 cSt. polydimethylsiloxane.sup.3. The
mixture is stirred until complete incorporation of the resin
mixture. Then 5.00 g of precipitated silica.sup.5 and 2.52 g fumed
silica.sup.6 is added and the mixture stirred until complete
incorporation of the silica is achieved.
Example 6: Silicone Antifoam Agent F1
Silicone antifoam agent F1 is prepared by charging a 250 ml
container equipped with a stirrer with 42.70 g of a polymer having
a molecular weight of approximately 65,000 and comprising 71-75
mole % dimethylsiloxane groups, 20-24 mole %
2-phenylpropylmethylsiloxane groups, 3-7 mole % octylmethylsiloxane
groups and terminated with a trimethylsilyl group.sup.1, 2.40 g of
an organosiloxane resin.sup.2 having trimethyl siloxane units and
SiO.sub.2 units in a M/Q ratio of about 0.65/1 to 0.67/1 dissolved
in 2.40 g of 2-ethylhexyl stearate.sup.4, 28.50 g of 10 cSt.
polydimethylsiloxane.sup.3 and 20.00 g of 7 cSt.
polydimethylsiloxane.sup.7. The mixture is stirred until complete
incorporation of the resin mixture. Then 4.00 g of precipitated
silica.sup.5 is added and the mixture stirred until complete
incorporation of the silica is achieved.
Example 7: Silicone Antifoam Agent G1
Silicone antifoam agent G1 is prepared by charging a 250 ml
container equipped with a stirrer with 65.52 g of a polymer having
a molecular weight of approximately 65,000 and comprising 71-75
mole % dimethylsiloxane groups, 20-24 mole %
2-phenylpropylmethylsiloxane groups, 3-7 mole % octylmethylsiloxane
groups and terminated with a trimethylsilyl group.sup.1 and 6.0 g
of an organosiloxane resin.sup.2 having trimethyl siloxane units
and SiO.sub.2 units in a M/Q ratio of about 0.65/1 to 0.67/1. The
mixture is stirred until complete incorporation of the resin. Then
5.25 g of Sipernat 35 precipitated silica.sup.5 and 1.75 g of
Aerosil 200 fumed silica.sup.5 is added and the mixture stirred
until complete incorporation of the silica is achieved. Then 0.79 g
of potassium methoxide is added and the mixture is stirred for 4
hours at 200.degree. C., cooled to ambient and 18.48 g of 10 cSt.
polydimethylsiloxane.sup.3 and 3.00 g of 2-ethylhexylstearate is
added and stirred until complete incorporation is achieved,
yielding a viscous semi-transparent liquid.
Example 8: Silicone Antifoam Agent H1
Silicone antifoam agent H1 is prepared by charging a 250 ml
container equipped with a stirrer with 70.56 g of a polymer having
a molecular weight of approximately 65,000 and comprising 71-75
mole % dimethylsiloxane groups, 27-33 mole %
2-phenylpropylmethylsiloxane groups, 3-7 mole % octylmethylsiloxane
groups and terminated with a trimethylsilyl group.sup.1, 3.80 g of
an organosiloxane resin.sup.2 having trimethyl siloxane units and
SiO.sub.2 units in a M/Q ratio of about 0.65/1 to 0.67/1 dissolved
in 3.00 g of 2-ethylhexyl stearate.sup.4 and 17.64 g of 10 cSt.
polydimethylsiloxane.sup.3. The mixture is stirred until complete
incorporation of the resin mixture. Then 5.00 g of precipitated
silica.sup.5 is added and the mixture stirred until complete
incorporation of the silica is achieved. .sup.1Supplied by
Shin-Etsu Silicones of America, Akron, Ohio.sup.2Supplied by Wacker
Silicones, Adrian, Mich. under the trade name Belsil.RTM.
803.sup.3Supplied by Shin-Etsu Silicones of America, Akron,
Ohio.sup.4Supplied by Wako Chemicals USA, Inc, Richmond,
Va..sup.5Available from Evonik Degussa Corporation, Parsippany,
N.J..sup.6Available from Evonik Degussa Corporation, Parsippany,
N.J..sup.7Available from Gelest, Inc., Morrisville, Pa.
Example 9: Synergistically Improved Rinse Suds Profile Achieved by
the Combination of Alkoxylated Polyalkoxyleneimine (PEI) with
Silicone Antifoam Agent (SA)
Four (4) sample liquid laundry detergent compositions are prepared,
which include: (A) a control composition that does not contain any
alkoxylated polyalkoxyleneimine or any antifoam premix; (B) a first
comparative composition formed by adding an alkoxylated
polyalkoxyleneimine of the present invention into the control
composition, but without any antifoam premix; (C) a second
comparative composition formed by adding the silicone antifoam
agent D1 of Example 4 into the control composition, but without any
alkoxylated polyalkoxyleneimine; and (D) an invention composition
formed by adding an alkoxylated polyalkoxyleneimine of the present
invention and the silicone antifoam agent 1 of Example 4 into the
control composition. Detailed compositional breakdown of these four
sample compositions are listed as follows in Table I:
TABLE-US-00001 TALBE I Sample Detergent Compositions (D) (A) (B)
(C) Control + Ingredients (wt %) Control Control + PEI Control + SA
PEI + SA C.sub.12-.sub.14AE.sub.1-3S 7.88 7.88 7.88 7.88
C.sub.11-.sub.13LAS 4.59 4.59 4.59 4.59 Neodol .RTM.25-7 a 0.61
0.61 0.61 0.61 C.sub.12-.sub.14 alkyl dimethyl amine 0.3 0.3 0.3
0.3 oxide Citric acid 2 2 2 2 Boric acid 1.2 1.2 1.2 1.2
C.sub.12-C.sub.18 fatty acid 1 1 1 1 Na-DTPA b 0.2 0.2 0.2 0.2 1,2
propanediol 2 2 2 2 Sodium cumene sulphonate 0 0 0 0 Silicone
(PDMS) emulsion 0.0025 0.0025 0.0025 0.0025 Monoethanolamine 0.096
0.096 0.096 0.096 NaOH Up to pH 8 Up to pH 8 Up to pH 8 Up to pH 8
Brightener 0.06 0.06 0.06 0.06 Neat perfume oil 0.55 0.55 0.55 0.55
Polyethyleneimine ethoxylate 0 2 0 2
(PEI.sub.600EO.sub.24PO.sub.16) Silicone Antifoam Agent (SA) 0 0
0.15 0.15 D1 of Example 4 Hydrogenated castor oil 0.12 0.12 0.12
0.12 Water Balance Balance Balance Balance
These four sample compositions are used to hand wash fabrics, in
order to observe the suds profile generated thereby during the
hand-washing process. For each sample composition, the following
hand washing test protocols are followed:
First, a red plastic basin of 40 cm in diameter and 19 cm in depth
is filled with 5 liters of water at room temperature that has a
water hardness of 12 gpg and a Ca/Mg ratio of 4:1. Twenty five (25)
grams of the sample liquid detergent composition is weighed and
poured into the basin. The wash solution is stirred by hand in a
circular motion for 10 times to ensure full dissolution. The
fabrics load to be washed by each sample liquid detergent
composition include: (1) 4 pieces of knitted cotton of 40
cm.times.40 cm in size and 125 g in weight, (2) a soiled cotton
swatch with the desired size of 10.5 cm.times.10.5 cm carrying 0.4
gram of clay particulates, and (3) a dirty white cotton shirt of
190 grams in weight collected from a consumer panel. The shirts
tested are all of the same brand and size and are worn by consumer
panels during the same period of time. Dirty shirts are selected
with similar soil level on collars to minimize variation.
Each knitted cotton piece, the soiled cotton swatch are washed by
hands with 10 times of scrubbing. The dirty shirt is washed by hand
with 20 times of scrubbing on the collar, and 10 times of scrubbing
on the torso section of the shirt. At the end of the wash, the
height of suds on the wash liquor surface is measured with a
ruler.
Subsequently, the 4 pieces of knitted cotton, the cotton swatch and
the shirt are removed from the wash liquor and squeezed to reach a
carry-over liquid weight of 990 g (i.e. 1440 g for total wet
fabrics).
To start the first rinse, the squeezed fabric load is placed into a
rinse basin containing 7 L of water having the same hardness as
described hereinabove. Three times of scrubbing are applied onto
each piece of fabric. After removal of the fabric, a picture is
taken from the top of the rinse basin. Suds floating on the surface
of the rinsing liquor can be classified into three different suds
coverage categories: (i) dense layer (opaque white, the red basin
bottom is blocked from sight); (ii) thin layer (translucent white,
the red basin bottom is vaguely visible), (iii) water layer (clear
water, the basin bottom is clearly visible). These three categories
of suds coverage render distinct intensity in grayscale imaging.
The denser the suds, the lighter the imaging intensity. The rinse
suds image is processed by an imaging analyzing software to
calculate the surface area of the dense suds layer (i), by counting
the number of pixels lighter than a defined threshold which
corresponds to the area where dense suds is present on the rinsing
liquor surface. The smaller the calculated surface area of the
dense suds layer, the more efficient is the sample composition in
reducing suds during the rinse.
Following Table II contains the calculated surface area (% over the
entire basin surface area) of the dense suds layer after rinse for
each of the four (4) sample liquid laundry detergent compositions
tested. Further, the measured results of the comparative samples
(B) and (C) as well as the inventive sample (D) are normalized over
that of the control sample (A) to provide a relative rinse suds
reduction index (.DELTA.E), which is calculated as the dense rinse
suds surface area of the sample composition minus the dense rinse
suds surface area of the control composition.
TABLE-US-00002 TABLE II (C) (D) (A) (B) Control + Control + Control
Control + PEI SA PEI + SA Dense Rinse Suds 45 19 41 2 Surface Area
(%) .DELTA.E (%) 0 26% 4% 43%
It is clear from the above results that the alkoxylated
polyalkyleneimine of the present invention and the silicone
antifoam agent containing the organomodified silicone and the
siloxane-based diluent act together to reduce rinse suds of the
control liquid laundry detergent composition in a synergistic
manner.
Example 10: Exemplary Liquid Laundry Detergent Compositions
Liquid laundry detergent compositions 10A-10E are made by mixing
together the ingredients listed in the proportions shown:
TABLE-US-00003 Ingredient (wt %) 10A 10B 10C 10D 10E
C.sub.12-C.sub.15 alkyl polyethoxylate (1.8) sulfate.sup.1 20.1
16.6 14.7 13.9 8.2 C.sub.11.8 linear alkylbenzene sulfonc
acid.sup.2 -- 4.9 4.3 4.1 8.2 C.sub.16-C.sub.17 branched alkyl
sulfate.sup.1 -- 2.0 1.8 1.6 -- C.sub.12 alkyl trimethyl ammonium
chloride.sup.4 2.0 -- -- -- C.sub.12 alkyl dimethyl amine
oxide.sup.5 0.7 0.6 -- -- C.sub.12-C.sub.14 alcohol 9
ethoxylate.sup.3 0.3 0.8 0.9 0.6 0.7 C.sub.15-C.sub.16 branched
alcohol-7 ethoxylate.sup.1 -- -- -- -- 4.6 1,2 Propane diol.sup.6
4.5 4.0 3.9 3.1 2.3 Ethanol 3.4 2.3 2.0 1.9 1.2 C.sub.12-C.sub.18
Fatty Acid.sup.5 2.1 1.7 1.5 1.4 3.2 Citric acid.sup.7 3.4 3.2 3.5
2.7 3.9 Protease.sup.7 (32 g/L) 0.42 1.3 0.07 0.5 1.12 Fluorescent
Whitening Agent.sup.8 0.08 0.2 0.2 0.17 0.18 Diethylenetriamine
pentaacetic acid.sup.6 0.5 0.3 0.3 0.3 0.2 Zwitterionic ethoxylated
quaternized -- 1.5 -- -- 0.8 sulfated hexamethylene diamine.sup.11
Hydrogenated castor oil.sup.12 0.2 0.2 0.12 0.3 Alkoxylated
Polyalkylenimine Polymer I.sup.9 0-4 1.8 1.5 1.0 -- Alkoxylated
Polyalkylenimine Polymer II.sup.10 0.5-5 -- 1.3 1.8 2.0 Silicone
Antifoam Agent A1-H1 0.2 0.3 0.15 0.25 0.4 Water, perfumes, dyes,
buffers, solvents to to to to to and other optional components 100%
100% 100% 100% 100% pH pH pH pH pH 8.0-8.2 8.0-8.2 8.0-8.2 8.0-8.2
8.0-8.2 .sup.1Available from Shell Chemicals, Houston, TX.
.sup.2Available from Huntsman Chemicals, Salt Lake City, UT.
.sup.3Available from Sasol Chemicals, Johannesburg, South Africa
.sup.4Available from Evonik Corporation, Hopewell, VA.
.sup.5Available from The Procter & Gamble Company, Cincinnati,
OH. .sup.6Available from Sigma Aldrich chemicals, Milwaukee, WI
.sup.7Available from Genencor International, South San Francisco,
CA. .sup.8Available from Ciba Specialty Chemicals, High Point, NC
.sup.9600 g/mol molecular weight polyethylenimine core with 20
ethoxylate groups per --NH and available from BASF (Ludwigshafen,
Germany). .sup.10600 g/mol molecular weight polyethylenimine core
with 24 ethoxylate groups per --NH and 16 propoxylate groups per
--NH. Available from BASF (Ludwigshafen, Germany). .sup.11Described
in WO 01/05874 and available from BASF (Ludwigshafen, Germany)
.sup.12Available under the tradename ThixinR from Elementis
Specialties, Highstown, NJ
Example 11: Liquid or Gel Detergents
Liquid or gel fabric care detergent compositions 11A-11E are
prepared by mixing the ingredients listed in the proportions
shown:
TABLE-US-00004 Ingredient (wt %) 11A 11B 11C 11D 11E
C.sub.12-C.sub.15 alkyl polyethoxylate (3.0) sulfate.sup.1 8.5 2.9
2.9 2.9 6.8 C.sub.11.8 linear alkylbenzene sulfonic acid.sup.2 11.4
8.2 8.2 8.2 1.2 C.sub.14-C.sub.15 alkyl 7-ethoxylate.sup.1 -- 5.4
5.4 5.4 3.0 C.sub.12-C.sub.14 alkyl 7-ethoxylate.sup.3 7.6 -- -- --
1.0 1,2 Propane diol 6.0 1.3 1.3 6.0 0.2 Ethanol -- 1.3 1.3 -- 1.4
Diethylene Glycol 4.0 -- -- -- -- Na Cumene Sulfonate -- 1.0 1.0
0.9 -- C.sub.12-C.sub.18 Fatty Acid.sup.5 9.5 3.5 3.5 3.5 4.5
Citric acid 2.8 3.4 3.4 3.4 2.4 Protease (40.6 mg/g/).sup.7 1.0 0.6
0.6 0.6 0.3 Natalase 200L (29.26 mg/g).sup.13 -- 0.1 0.1 0.1 --
Termamyl Ultra (25.1 mg/g).sup.13 0.7 0.1 0.1 0.1 0.1 Mannaway 25L
(25 mg/g).sup.13 0.1 0.1 0.1 0.1 0.02 Whitezyme (20 mg/g).sup.13
0.2 0.1 0.1 0.1 -- Fluorescent Whitening Agent.sup.8 0.2 0.1 0.1
0.1 -- Diethylene Triamine Penta Methylene -- 0.3 0.3 0.3 0.1
Phosphonic acid Hydroxy Ethylidene 1,1 Di Phosphonic 1.5 -- -- --
-- acid Zwitterionic ethoxylated quaternized 2.1 1.0 1.0 1.0 0.7
sulfated hexamethylene diamine.sup.11 PEG-PVAc Polymer.sup.14 0.9
0.5 0.5 0.5 -- Hydrogenated castor oil.sup.12 0.8 0.4 0.4 0.4 0.3
Borate -- 1.3 -- -- 1.2 4 Formyl Phenyl Boronic Acid -- -- 0.025 --
-- Alkoxylated Polyalkyleneimine I.sup.9 0-4 1.8 1.5 1.0 --
Alkoxylated Polyalkyleneimine II.sup.10 0.5-5 -- 1.3 1.8 2.0
Silicone Antifoam Agent A1-H1 0.4 0.3 0.3 0.2 0.3 Water, perfumes,
dyes, buffers, to to to to to neutralizers, stabilizers and other
optional 100% 100% 100% 100% 100% components pH pH pH pH pH 8.0-8.2
8.0-8.2 8.0-8.2 8.0-8.2 8.0-8.2 .sup.13Available from Novozymes,
Copenhagen, Denmark. .sup.14PEG-PVA graft copolymer is a polyvinyl
acetate grafted polyethylene oxide copolymer available from BASF
(Ludwigshafen, Germany), having a polyethylene oxide backbone and
multiple polyvinyl acetate side chains. The molecular weight of the
polyethylene oxide backbone is about 6000 and the weight ratio of
the polyethylene oxide to polyvinyl acetate is about 40 to 60.
Example 12: Rinse-Added Fabric Care Compositions
Rinse-Added fabric care compositions 12A-12D are prepared by mixing
together ingredients shown below:
TABLE-US-00005 Ingredients (wt %) 12A 12B 12C 12D Fabric Softener
Active.sup.15 16.2 11.0 16.2 -- Fabric Softener Active.sup.16 -- --
-- 5.0 Cationic Starch.sup.17 1.5 -- 1.5 -- Quaternized
polyacrylamide.sup.18 -- 0.25 0.25 Calcium chloride 0.15 0. 0.15 --
Ammonium chloride 0.1 0.1 0.1 -- Alkoxylated Polyalkyleneimine
I.sup.9 0-4 1.8 1.5 -- Alkoxylated Polyalkyleneimine 0.5-5 -- 1.3
1.8 II.sup.10 Silicone Antifoam Agent A1-H1 0.2 0.15 0.25 0.3
Perfume 0.85 2.0 0.85 1.0 Perfume microcapsule.sup.19 0.65 0.75
0.65 0.3 Water, suds suppressor, to 100% to 100% to 100% to 100%
stabilizers, pH control agents, pH = pH = pH = pH = buffers, dyes
& other optional 3.0 3.0 3.0 3.0 ingredients .sup.15N,N
di(tallowoyloxyethyl)-N,N dimethylammonium chloride available from
Evonik Corporation, Hopewell, VA. .sup.16Reaction product of fatty
acid with Methyldiethanolamine, quaternized with Methylchloride,
resulting in a 2.5:1 molar mixture of N,N-di(tallowoyloxyethyl)
N,N-dimethylammonium chloride and N-(tallowoyloxyethyl)
N-hydroxyethyl N,N-dimethylammonium chloride available from Evonik
Corporation, Hopewell, VA. .sup.17Cationic starch based on common
maize starch or potato starch, containing 25% to 95% amylose and a
degree of substitution of from 0.02 to 0.09, and having a viscosity
measured as Water Fluidity having a value from 50 to 84. Available
from National Starch, Bridgewater, NJ. .sup.18Cationic
polyacrylamide polymer such as a copolymer of
acrylamide/[2-(acryloylamino)ethyl]tri-methylammonium chloride
(quatemized dimethyl aminoethyl acrylate) available from BASF, AG,
Ludwigshafen under the trade name Sedipur 544. .sup.19Available
from Appleton Paper of Appleton, WI.
Example 13: Powder Laundry Detergent Compositions
Powder laundry detergent compositions 13A-13C are prepared by
mixing together ingredients shown below:
TABLE-US-00006 Ingredient (wt %) 13A 13B 13C LAS (Non-sulphated
anionic 10 15-16 7 surfactant) Mixture of alkyl sulphate
surfactants 1.5 1.5-2 1.5 Cationic surfactant 0-1 0-1.5 0-1
Non-ionic surfactant 0-1 0-1.5 0-1 Zeolite 0-3 6-10 0-3 Bleach and
bleach activator 0-5 4-6 2-3 Silicate 7-9 -- 5-6 Carbonate 10-30
25-35 15-30 Sulfate 30-70 30-35 40-70 Alkoxylated polyalkyleneimine
I 0.5-5 1-4 2-3 and/or II Silicone antifoam agent A1-H1 0.1-2
0.15-1 0.2-0.5 Deionized water Balance to 100 wt %
Example 14: Liquid Dish Detergent Compositions
Liquid dish detergent compositions 14A-13G are prepared by mixing
together ingredients shown below:
TABLE-US-00007 Ingredients (wt %) 14A 14B 14C 14D 14E 14F 14G Alkyl
C.sub.10-14 Ethoxy 26.9 -- -- 25.7 -- 11.1 21.0 Sulphate (AE0.6S)
Alkyl C.sub.10-14 Ethoxy -- 18.7 26.9 -- 18.7 -- -- Sulphate (AE2S)
Sodium alkyl -- 8.0 -- -- -- -- -- benzene sulfonate Sodium
paraffin -- -- -- -- 8.0 -- -- sulfonate C12-14 dimethyl 6.1 -- --
4.1 -- 3.7 10.0 amine oxide Cocamido propyl -- 4.5 6.8 3.2 6.0 --
-- betaine C12-13 EO7 nonionic -- -- -- -- -- 1.0 2.0 Branched
Nonionic: 1.0 0.8 -- -- -- -- 1.0 3-propyl heptanol EO8 Ethanol 4.0
5.0 3.0 3.0 2.0 -- 3.0 Polypropylene glycol 1.1 0.8 1.1 1.1 1.1 0.5
1.1 MW2000 Sodium Chloride 1.3 0.8 1.3 0.5 0.8 1.3 1.3 Alkoxylated
.sup. 0-4 1.0 2 1.0 1.3 -- -- Polyalkyleneimine I Alkoxylated 0.5-5
-- -- 1.5 1.5 2 4 Polyalkyleneimine II Silicone Antifoam 0.1-2 0.15
0.25 0.3 0.2 0.15 0.25 Agent A1-H1 Minors* and water to balance up
to 100%
Every document cited herein, including any cross referenced or
related patent or application, is hereby incorporated herein by
reference in its entirety unless expressly excluded or otherwise
limited. The citation of any document is not an admission that it
is prior art with respect to any invention disclosed or claimed
herein or that it alone, or in any combination with any other
reference or references, teaches, suggests or discloses any such
invention. Further, to the extent that any meaning or definition of
a term in this document conflicts with any meaning or definition of
the same term in a document incorporated by reference, the meaning
or definition assigned to that term in this document shall
govern.
While particular embodiments of the present invention have been
illustrated and described, it would be obvious to those skilled in
the art that various other changes and modifications can be made
without departing from the spirit and scope of the invention. It is
therefore intended to cover in the appended claims all such changes
and modifications that are within the scope of this invention.
* * * * *